From F energy rating to Nearly ZEB: project of energy retrofit and architectural upgrade of a brick terraced house in Co. Dublin, Ireland

Questo progetto è stato sviluppato durante un periodo di ricerca presso il Dipartimento di Ingegneria Civile del Trinity College e continuato presso l’Università di Bologna. Il progetto ha l’obiettivo di analizzare le soluzioni per l’ampliamento, la sostituzione degli impianti e l’ottimizzazione energetica di un tipico edificio residenziale Irlandese, una end of terrace in mattoni costruita negli anni ’20, collocata a Blackrock (Dublino). Diversi studi sostengono che lo stock abitativo irlandese è il peggiore del nord Europa per quanto riguarda la performance energetica. Questa tesi consta di una prima parte di studio del contesto e delle tecniche costruttive tradizionali irlandesi; è presente un capitolo di approfondimento sulle leggi riguardanti le costruzioni e gli incentivi forniti dal governo irlandese per interventi di retrofit energetico. Il terzo capitolo è un’analisi dell'esistente, con disegni del rilievo geometrico, immagini dell’edificio originale, termogrammi e dati riguardanti l’attuale performance energetica. Vengono poi mostrate diverse ipotesi di progetto e, una volta determinata la disposizione degli spazi interni, vengono considerate due soluzioni simili, ma costruite con pacchetti costruttivi diversi. Nel Progetto A l’involucro dell’addizione ha una struttura in muratura, nel Progetto B la struttura è in X-lam. Le performance energetiche delle due proposte vengono confrontate tramite una simulazione attuata grazie all'utilizzo del software dinamico IES-VE. Viene valutata l’applicazione di energie rinnovabili, quali l’energia solare e eolica e l’apporto che queste possono dare al bilancio energetico. Infine viene fatta un’analisi dei costi, valutando possibili suddivisioni dei lavori e ipotizzando un piano di ritorno dell’investimento, anche in combinazione con l’applicazione di energie rinnovabili. Alla fine del progetto si trova una valutazione quantitativa dei miglioramenti dell’edificio e un’analisi critica dei limiti del progetto.

Synthesis, characterization and catalytic performances of ruthenium-based catalysts for the acceptorless dehydrogenative coupling of butanol

A growing interest towards new sources of energy has led in recent years to the development of a new generation of catalysts for alcohol dehydrogenative coupling (ADC). This green, atom-efficient reaction is capable of turning alcohol derivatives into higher value and chemically more attractive ester molecules, and it finds interesting applications in the transformation of the large variety of products deriving from biomass. In the present work, a new series of ruthenium-PNP pincer complexes are investigated for the transformation of 1-butanol, one of the most challenging substrates for this type of reactions, into butyl butyrate, a short-chain symmetrical ester widely used in flavor industries. Since the reaction kinetics depends on hydrogen diffusion, the study aimed at identifying proper reactor type and right catalyst concentration to avoid mass transfer interferences and to get dependable data. A comparison between catalytic activities and productivities has been made to establish the role of the different ligands bonded both to the PNP binder and to the ruthenium metal center, and hence to find the best catalyst for this type of reaction.

Determination of local density of states in amorphous oxide semiconductors with Kelvin Probe Force Microscopy

Amorphous semiconductors are important materials as they can be deposited by physical deposition techniques on large areas and even on plastic substrates. Therefore, they are crucial for transistors in large active matrices for imaging and transparent wearable electronics. The most widely applied candidate for amorphous thin film transistors production is Indium Gallium Zinc Oxide (IGZO). It is attracting much interest because of its optical transparency, facile processing by sputtering deposition and notable improved charge carrier mobility with respect to hydrogenated amorphous silicon a-Si:H. Degradation of the device and long-term performance issues have been observed if IGZO thin film transistors are subjected to electrical stress, leading to a modification of IGZO channel properties and subthreshold slope. Therefore, it is of great interest to have a reliable and precise method to study the conduction band tail, and the density of states in amorphous semiconductors. The aim of this thesis is to develop a local technique using Kelvin Probe Force Microscopy to study the evolution of IGZO DOS properties. The work is divided into three main parts. First, solutions to the non-linear Poisson-Boltzmann equation of a metal-insulator-semiconductor junction describing the charge accumulation and its relation to DOS properties are elaborated. Second macroscopic techniques such as capacitance voltage (CV) measurements and photocurrent spectroscopy are applied to obtain a non-local estimate of band-tail DOS properties in thin film transistor samples. The third part of my my thesis is dedicated to the KPFM measurements. By fitting the data to the developed numerical model, important parameters describing the amorphous conduction band tail are obtained. The results are in excellent agreement with the macroscopic characterizations. KPFM result is comparable also with non-local optoelectronic characterizations, such as photocurrent spectroscopy.

Ab-initio determination of x-ray absorption near edge structure (xanes) spectra in an ultrasoft and norm conserving pseudopotentials scheme

X-ray absorption spectroscopy (XAS) is a powerful means of investigation of structural and electronic properties in condensed -matter physics. Analysis of the near edge part of the XAS spectrum, the so – called X-ray Absorption Near Edge Structure (XANES), can typically provide the following information on the photoexcited atom: - Oxidation state and coordination environment. - Speciation of transition metal compounds. - Conduction band DOS projected on the excited atomic species (PDOS). Analysis of XANES spectra is greatly aided by simulations; in the most common scheme the multiple scattering framework is used with the muffin tin approximation for the scattering potential and the spectral simulation is based on a hypothetical, reference structure. This approach has the advantage of requiring relatively little computing power but in many cases the assumed structure is quite different from the actual system measured and the muffin tin approximation is not adequate for low symmetry structures or highly directional bonds. It is therefore very interesting and justified to develop alternative methods. In one approach, the spectral simulation is based on atomic coordinates obtained from a DFT (Density Functional Theory) optimized structure. In another approach, which is the object of this thesis, the XANES spectrum is calculated directly based on an ab – initio DFT calculation of the atomic and electronic structure. This method takes full advantage of the real many-electron final wavefunction that can be computed with DFT algorithms that include a core-hole in the absorbing atom to compute the final cross section. To calculate the many-electron final wavefunction the Projector Augmented Wave method (PAW) is used. In this scheme, the absorption cross section is written in function of several contributions as the many-electrons function of the finale state; it is calculated starting from pseudo-wavefunction and performing a reconstruction of the real-wavefunction by using a transform operator which contains some parameters, called partial waves and projector waves. The aim of my thesis is to apply and test the PAW methodology to the calculation of the XANES cross section. I have focused on iron and silicon structures and on some biological molecules target (myoglobin and cytochrome c). Finally other inorganic and biological systems could be taken into account for future applications of this methodology, which could become an important improvement with respect to the multiscattering approach.

Heat-transfer enhancement with pulsed jets in turbulent pipe flow at high-Reynolds number

Improving heat transfer is a critical area of ​​research in various fields such as thermal engineering, energy conversion and aeronautical engineering. The aim of this thesis is to present the design, construction and testing of an experimental setup for the study of heat transfer enhancement in a turbulent boundary layer using cross-flow pulsed jets. The set-up is designed to generate and control pulsed jets, measure heat transfer and acquire all parameters related to wind tunnel flow and is also capable of varying the parameters of the pulsed jets, such as frequency, amplitude and the duty cycle, in order to study the effects on the increase in heat transfer. The thesis describes the design phases, the construction process and the final successful testing of the plant. The test results verify the functionality and accuracy of the set-up and ensure that it can be used to perform a full experimental campaign to investigate heat transfer enhancement using cross-flow pulsed jets in a turbulent layer boundary.